KR20230019058A - Method for producing high nickel lithiated metal oxide for battery - Google Patents

Abstract

Provided is a method for preparing a high nickel lithiated metal oxide, which includes selecting one or more nickel precursors, at least one non-corrosive lithium salt, and a plurality of metal oxides or hydroxide precursors. A metal precursor and a lithium salt are mixed together to form a mixture containing Li_xNi_yM_zN_(1-y-z)O_(2-a)F_a(F-1) (where x=1.0 to 1.1, 0.80<=y<=0.90, 0.03<z<=0.15, 0<=a<=0.05, M is Co or Fe, and N is Al, Mn, Fe, Ca, Mg, Ti, Cr, Nb, Mo, W, B or a mixture thereof, wherein N may be Fe when M is Co). The mixture is subjected to sintering (primary step) in the air at 750℃ or higher to form powder. The powder is subjected to a secondary sintering step in O_2 at 750℃ or lower to form the high nickel lithiated metal oxide.

Description

Method for producing high nickel lithiated metal oxide for battery {METHOD FOR PRODUCING HIGH NICKEL LITHIATED METAL OXIDE FOR BATTERY}

The present invention generally relates to a method of making a cathode active material for use in an electrochemical cell such as a battery. More specifically, the present invention describes methods for producing high nickel or nickel rich lithiated metal oxides.

The descriptions in this section merely provide background information related to the present disclosure and may not constitute prior art.

In existing processes used to make lithium ion batteries, high nickel cathode materials such as Li _x Ni _y Co _z M _(1-yz) O ₂ where M is aluminum (Al) and/or manganese (Mn); x ≥ 0.8, and y ≤ 0.15) must be created using lithium hydroxide (LiOH) as the lithium source in an oxygen (O ₂ ) environment at high temperatures (eg, ≥ 700° C.). In a typical manufacturing process, Ni(II) sulfate, Co(II) sulfate, Al(III) sulfate and/or Mn(II) sulfate are dissolved in water and then coprecipitated by the addition of a mixture of sodium and ammonium hydroxide. . The precipitated hydroxide material is then washed, dried and blended with LiOH ^* H ₂ O. The resulting blend or mixture is sintered at 750° C. in an O ₂ environment to form a lithiated high nickel metal oxide.

In this process, O ₂ is required because the nickel groups in the lithiated metal oxide must be in a high oxidation state (eg, Ni ³⁺ ), whereas the starting Ni(II) sulphate precursor ^{yields nickel whose oxidation state is Ni 2+ .} include It is very difficult to oxidize Ni ²⁺ to Ni ³⁺ at ^high temperatures, so _{a high O 2} ^partial pressure is required during the sintering process. This is also one of the main reasons for choosing and using LiOH instead of other lithium precursors such as Li ₂ CO ₃ . When Li ₂ CO ₃ is used, CO ₂ is released during sintering to lower the O ₂ partial pressure and consequently, the intermixing content of Ni ²⁺ and Li ^{+ ions} in the resulting metal oxide increases.

LiOH is also commonly used because of its low melting point (i.e., about 462°C). The process using LiOH can form fully lithiated metal oxides at relatively low temperatures (700 to 800 °C), since molten LiOH increases the contact area between the lithium salt and the mixed metal oxide particles, resulting in a lithiation reaction. because it promotes By comparison, the melting point of Li ₂ CO ₃ is 723 °C and a sintering temperature >800 °C is required when lithium carbonate is used as the lithium salt.

In addition, high nickel lithiated metal oxides have poor thermal stability, so the sintering temperature of the process cannot be maintained at a high level. More specifically, high nickel lithiated metal oxides decompose at high temperatures to form Li _(1-x) Ni _(1+x) O ₂ and release O ₂ . Thus, for use in commercial production of high nickel lithium metal oxide cathode materials, LiOH is generally chosen over Li ₂ CO ₃ because of its lower sintering temperature and no CO ₂ production during sintering.

Unfortunately, at the sintering temperatures commonly used in production processes, LiOH is highly corrosive to furnace and crucible metal components. The resulting corrosion rates encountered during production generally result in significant and undesirable increases in production costs. To increase efficiency and lower production costs, it is desirable to replace LiOH with a non-corrosive salt.

The present disclosure generally relates to methods of making cathode active materials for use in electrochemical cells such as batteries. More specifically, the present invention describes methods for producing high nickel or nickel rich lithiated metal oxides.

Methods for producing high nickel lithiated metal oxides generally include:

a. selecting one or more nickel precursors;

b. providing at least one non-corrosive lithium salt;

c. delivering a plurality of metal oxide or hydroxide precursors;

d. mixing together one or more nickel precursors, one or more non-corrosive lithium salts, and a plurality of metal oxide/hydroxide precursors to form a mixture comprising:

where x = 1.0 - 1.1, 0.80 ≤ y ≤ 0.90, 0.03 < z ≤ 0.15, and 0 ≤ ≤ 0.05, M is Co or Fe; and N is Al, Mn, Fe, Ca, Mg, Ti, Cr, Nb, Mo, W, B, or mixtures thereof, provided that when M is Co, N may be Fe;

e. Forming a powder by sintering the mixture at a temperature of 750 ° C. or higher in an air environment in the first sintering step;

f. In the secondary sintering step, the powder is sintered in an O ₂ environment at a temperature of 750° C. or less to form a high nickel lithiated metal oxide.

According to another aspect of the present disclosure, a cathode active material for use in a battery includes a material formed according to the process described above and further defined herein having a composition according to Formula (F-1).

According to another aspect of the present invention, there is provided a lithium ion or lithium battery comprising a cathode active material having a composition according to Formula (F-1).

Additional areas of applicability will become apparent from the description provided herein. It should be understood that the descriptions and specific examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure.

In order that the present disclosure may be better understood, various forms provided by way of example will now be described with reference to the accompanying drawings. The elements of each drawing may not necessarily be drawn to scale, but rather focus on illustrating the principles of the present invention.
1 is a flow diagram illustrating a two-step sintering process for producing a high nickel or nickel rich lithiated metal oxide, in accordance with the teachings of the present disclosure.
2A and 2B show x-ray diffraction (XRD) patterns measured for NCA80 (FIG. 2A) and NCA90 (FIG. 2B) prepared according to the teachings of the present disclosure and sintered under different conditions.
FIG. 3 shows additional x-ray diffraction measurements for NCA80 sintered using a first sintering step (800° C.) in an air environment with or without a second sintering step (750° C.) in an oxygen (O ₂ ) environment. (XRD) shows the pattern.
Figure 4 is another X-ray diffraction (XRD) analysis of NCMA90 sintered using a first sintering step (800 °C) in an air environment with or without exposure to a second sintering step (750 °C) in an oxygen (O ₂ ) environment. show the pattern.
The drawings described herein are for illustrative purposes only and are not intended to limit the scope of the present disclosure in any way. Throughout the description and drawings, corresponding reference numbers are to be understood as indicating like or corresponding parts and features.

The following description is merely illustrative in nature and is in no way intended to limit the disclosure or its application or uses. For example, high nickel or nickel rich lithiated metal oxides prepared and used according to the teachings contained herein will be used throughout this disclosure as cathode active materials used with batteries to more fully demonstrate their structural elements and uses. are listed The incorporation and use of such high nickel lithiated metal oxides in other applications, including without limitation as at least part of an electrode in another electrochemical cell, is considered within the scope of this disclosure.

For purposes of this disclosure, the terms “about” and “substantially” are used herein with reference to measurable values and ranges due to expected variations known to those skilled in the art (eg, limits and variations of measurements).

For purposes of this disclosure, the terms “at least one” and “one or more” elements are used interchangeably and may have the same meaning. These terms indicating the inclusion of a single element or multiple elements may also be indicated by the suffix "(s)" at the end of the element. For example, "at least one metal", "one or more metals" and "metal(s)" may be used interchangeably and are intended to have the same meaning.

The present disclosure generally provides a two-step process for producing high nickel or nickel-rich lithium metal oxide for use as a cathode active material using one or more non-corrosive lithium salts. Referring to FIG. 1 , this process 1 includes selecting one or more nickel precursors, providing at least one non-corrosive lithium salt, and delivering a plurality of metal oxide/hydroxide precursors, whereby the metal At least one oxide/hydroxide precursor comprises cobalt (Co), iron (Fe) or a combination thereof and at least another metal precursor comprises aluminum (Al), manganese (Mn), calcium (Ca), magnesium (Mg), titanium (Ti), chromium (Cr), niobium (Nb), molybdenum (Mo), tungsten (W), boron (B), or combinations thereof.

One or more nickel precursors, one or more non-corrosive lithium salts, and a plurality of metal oxide/hydroxide precursors are mixed together to form a mixture comprising, consisting of, or consisting essentially of formula (F-1):

where x is in the range of 1.0 - 1.1, 0.80 ≤ y ≤ 0.90, 0.03 < z ≤ 0.15, and 0 ≤ ≤ 0.05; M is Co or Fe; and N is Al, Mn, Fe, Ca, Mg, Ti, Cr, Nb, Mo, W, B, or combinations thereof, provided that N may be Fe when M is Co. Alternatively, in formula (F-1), 0.80 ≤ y ≤ 0.87; Alternatively, 0.80 ≤ y ≤ 0.85. Fluorine (F) may be intentionally present or included as an impurity. Alternatively, F may be absent, ie a = 0, and formula (F-1) may be expressed as Li _x Ni _y M _z N _(1-yz) O ₂ . N in Formula (F-1) may alternatively be Al, Mn, Fe, Mo, or combinations thereof. When Al and Mn are present in combination, the molar ratio of Al:Mn ranges from 0.99/0.01 to 0.01/0.99; alternatively, in the range of 0.2/0.8 to 0.8/0.2; and alternatively, from 0.3/0.7 to 0.7/0.3. When Al, Mn, and one of Mo or Fe is present in combination, the ratio of Al to Mn to Fe or Mo [Al:Mn:(Fe-Mo)] is 0.99/0.05/0.05 or 0.05/0.99/0.05 or It can range from 0.05/0.05/0.99. Alternatively, the ratio of Al:Mn:(Fe or Mo) is in the range of 0.1/0.8/0.1 or 0.8/0.1/0.1 or 0.1/0.1/0.8, and alternatively 0.15/0.7/0.15 or 0.7/0.15 It is in the range of /0.15 or 0.15/0.15/0.7.

The non-corrosive lithium salt may be selected from lithium acetate, lithium nitrate, lithium oxalate, lithium carbonate or mixtures thereof. Alternatively, the non-corrosive salt is lithium carbonate (Li ₂ CO ₃ ).

The cobalt or iron precursor (M) is, without limitation, Co ₃ O ₄ , CoO, Co(OH) ₂ , CoOOH, cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt nitrate, Fe ₃ O ₄ , Fe ₂ O ₃ , FeO, FeOOH , Fe(OH) ₃ , Fe(OH) ₂ , iron carbonate, iron acetate, iron oxalate, iron nitrate or similar materials. Alternatively, the cobalt or iron precursor may include Co ₃ O ₄ , CoO, Fe ₃ O ₄ , or Fe ₂ O ₃ . Alternatively, the cobalt precursor is Co ₃ O ₄ . Iron precursors can also be used for N when M is Co.

Other metal oxides or metal hydroxide precursors (N) that can be used include, for example, Al ₂ O ₃ , Al(OH) ₃ , aluminum acetate, aluminum carbonate, aluminum oxalate, aluminum ethoxide, aluminum propyl oxide, aluminum butyl oxide, B ₂ O ₃ , B ₂ O ₅ , H ₃ BO ₃ , boron acetate, and borates. The metal oxide or metal hydroxide precursor can be a metal oxide, a metal hydroxide, or a metallic compound that decomposes into a metal oxide or metal hydroxide. Alternatively, the metal oxide or metal hydroxide precursor (N) includes Al(OH) _{3 ,} and/or H ₃ BO ₃ .

Nickel precursors may include, but are not limited to, nickel oxide, nickel hydroxide, nickel oxyhydroxide, nickel acetate, nickel carbonate, and nickel oxalate. If preferred, nickel oxide is applied in 3 to 6 hours; Alternatively, it may be formed by decomposing Ni(NO ₃ ) ₂ ^* 6H ₂ O at high temperature for a time ranging from about 4 to 5 hours. Alternatively, the nickel precursor is nickel oxide.

Nickel precursors, non-corrosive lithium salts, and metal oxide/hydroxide precursors may be prepared in a batch or continuous manner, including, but not limited to, for example, a ball mill, an atliter mill, a jet mill, a plowshare mixer, or similar equipment. They can be mixed using a mixing system. Alternatively, the material is milled into 1 to 20 mm beads (oxide/bead mass ratio 1/3) in a solid/liquid ratio of about 4/6 with a liquid medium (e.g., water) using a ball mill for 1 to 24 hours. ; Alternatively, it is mixed for a period of about 5 hours. Alternatively, the material is mixed using a ball mill without liquid medium at an oxide/bead ratio ranging from 1/1 to 1/20 and a bead size ranging from 1 mm to 20 mm for 1 to 24 hours. Alternatively, the materials are mixed by blending together without any beads for a period of 1 to 24 hours.

After mixing, the mixture is collected and dried by any means known to those skilled in the art including, but not limited to, subjecting to a thermal environment such as an oven to remove any liquid or moisture and filtering. Alternatively, the mixture may be spray dried by conventional methods known to those skilled in the art.

Referring back to FIG. 1 , the first (primary) sintering or presintering step exposes a mixture of the non-corrosive lithium salt, the nickel precursor, and the metal oxide/hydroxide precursor to high temperature to decompose and lithiate the non-corrosive lithium salt. This is done by decomposing the metal oxide to a high Li ⁺ /Ni ²⁺ mixed content ^. The temperature of this first sintering step is generally 750° C. or higher; alternatively, >800°C; or alternatively, >850°C; Alternatively, ≥ 750 ° C to ≤ 1000 ° C; Alternatively, ≥ 800 ° C to ≤ 950 ° C; Alternatively, it ranges from ≥ 850 °C to ≤ 900 °C. The sintering environment for the pre-sintering step may be air, and the length of time for the first sintering step ranges from 2 hours to 24 hours; alternatively, from about 5 hours to about 20 hours; alternatively, in the range of 7 hours to 15 hours; Alternatively, about 10 hours.

Still referring to FIG. 1 , after the presintering or primary sintering step, the lithiated metal oxide is then treated by further sintering in a second (secondary) sintering or post-treatment step in a relatively low temperature O ₂ environment to obtain any The residual Ni ²⁺ is oxidized to Ni ³⁺ , ^and the Ni ³⁺ distribution is reconstituted in the nickel ^- rich lithium metal oxide to reduce the mixed content ^of Li ⁺ /Ni ^{2+ .} The sintering temperature for this secondary sintering step is generally < 750 °C; Alternatively, ≤ 750 °C to ≥ 700 °C. For purposes of this disclosure, an O ₂ environment refers to an environment in which the partial pressure of O ₂ is greater than that found in air. Alternatively, the oxygen environment may be pure O ₂ . The length of time of the secondary sintering step ranges from 2 hours to 24 hours; alternatively, from about 5 hours to about 20 hours; alternatively, in the range of 7 hours to 15 hours; Alternatively, about 10 hours. According to one aspect of the present disclosure, the sintering time of the second sintering step is longer than the sintering time of the first sintering step.

High nickel lithiated metal oxides are characterized using x-ray diffraction with measurements performed on a benchtop Rigaku x-ray machine equipped with Cu Kα radiation using an operating voltage of 30 kV and a current of 15 mA. The x-ray diffraction (XRD) peak ratio of (003)/(104 ⁾ is used as an index for the mixed content of Li ⁺ /Ni ²⁺ . A higher peak ratio of (003)/(104) indicates a lower ^cation mixing content between Li ⁺ and Ni ²⁺ , which infers better electrochemical performance. The (003) peak arises from the diffraction of the stratified halite structure, whereas the (104) peak appears due to the diffraction of both the stratified halite structure and the cubic halite structure. When the Li ⁺ and Ni ^{2+ ions} are completely mixed, the (003) reflection intensity should be zero.

The high nickel lithiated metal oxide may have a nickel (Ni) content ranging from about 80 mole % to less than 90 mole % relative to the total metal content present in the nickel rich lithiated metal oxide. Alternatively, the nickel content is 80 mol % to 85 mol %. The cobalt (Co) and/or iron (Fe) content is from 1 mole % to 20 mole % relative to the total metal content present in the nickel rich lithiated metal oxide. Alternatively, the cobalt or iron content is between 5 and 15 mole percent.

The specific examples provided in this disclosure are provided to illustrate various embodiments of the invention and should not be construed as limiting the scope of the disclosure. Although the embodiments have been described in a manner that allows for a clear and concise description, it is intended and will be appreciated that the embodiments may be variously combined or separated without departing from the invention. For example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

Example 1. LiNi _{0 . 8} Co _{0 . 15} Al ₀ . ₀₅ O ₂ (NCA80) and LiNi _{0 . 9} Co _{0 . 05} Al _{0 .} Manufacturing and testing of ₀₅ O ₂ (NCA90)

Ni(NO ₃ ) ₂ ^* 6H ₂ O was decomposed at 600° C. for 4 hours in an air environment to produce more than 100 grams of nickel oxide (NiO). LiNi _{0 . 8} Co _{0 . 15} Al ₀ . ₀₅ O ₂ For (NCA80), 19.40 grams of Li ₂ CO ₃ , 29.88 grams of NiO, 6.02 grams of Co ₃ O ₄ , and 1.95 grams of Al(OH)3 were combined with a solid/water mass ratio of 4/6 and a solid/water mass ratio of 1/3. Ball milled for 5 hours at an oxide/bead mass ratio. To make LiNi _0.9 Co _0.05 Al _0.05 O ₂ (NCA90), 33.61 g NiO was ball milled in water with Li ₂ CO ₃ , 2.01 g Co ₃ O ₄ , and 1.95 g Al(OH) ₃ for 5 hours. did The solid/water mass ratio was 4/6. The milled slurry was then spray dried. The dried powder was sintered under various conditions as described in Table 1.

An x-ray diffraction (XRD) peak ratio of (003)/(104) was also measured for the resulting high nickel lithiated meal oxide as shown in Table 1. The measured X-ray diffraction (XRD) patterns for NCA80 and NCA90 are also provided in FIGS. 2A and 2B for comparison. The NCA80 sample contained 80 mol% nickel compared to all non-lithium metal, while the NCA90 sample contained 90 mol% nickel compared to non-lithium metal.

Table 1: Sintering conditions and peak ratio (003)/(104) for NCA80 and NCA90.

As shown in Table 1, the peak ratio between (003)/(104) is _NCA80 sample ( 80 mol% nickel). When the sintering step was performed only in air (850 °C), the NCA80 sample exhibited a lower peak ratio of (003)/(104) than the sample treated in O ₂ sintered at a lower temperature of 750 °C (i.e., 0.95 vs 1.25). This result is expected due to the decrease in O ₂ partial pressure that occurs when sintering in air. When sintered in O ₂ only, the sample treated at 850 °C showed a lower peak ratio of (003)/(104) than the sample treated at 750 °C. This result is also expected because of the poor thermal stability of high nickel lithiated metal oxides. For samples sintered at 850 °C and then treated in O ₂ at 750 °C, the (003)/(104) peak ratio was 1.47, which was higher than samples sintered at 750 °C or 850 °C in O ₂ . This result confirms that the O ₂ treatment at 750° C. oxidized the Ni ²⁺ impurities from the 850° C. air sintered sample, ^and furthermore, the Li/Ni mixing level was lower than that of the sample sintered in O ₂ . Thus, using a post-treatment (secondary) sintering step in O ₂ at a lower temperature than the first presintering step reduces Li ⁺ /Ni ²⁺ mixing and redistributes Ni3 ⁺ ions.

Still referring to Table 1, the same effect of post-treatment in O ₂ was not observed when the Ni content was increased to 90 mol% (see NCA90). In this case, the use of post-treatment in O ₂ actually reduced the (003)/(104) peak ratio to values well below those measured for samples sintered in air (compare 0.82 vs. 0.99). This result suggests that at this nickel concentration, the two ^- step sintering process is not effective in maintaining low Li ⁺ /Ni ²⁺ mixing levels.

Example 2 - LiNi _{0 . 8} Co _{0 . 15} Al ₀ . ₀₅ O ₂ Further fabrication and testing of (NCA80)

NCA80 was prepared under the same conditions as the materials discussed in Example 1, except that the first sintering temperature was 800°C instead of 850°C. The dried powder was finally sintered under various conditions listed in Table 2. X-ray diffraction (XRD) peak ratios of (003)/(104) were also measured for the resulting high nickel lithiated meal oxide as shown in Table 1. The NCA80 sample contained 80 mole % nickel.

The x-ray diffraction (003)/(104) peak ratio shown in Table 2 shows the same trend as that observed in Table 1. Samples sintered with the first sintering step in air (800 °C) and the second step of O ₂ sintering (750 °C) have significantly higher (003)/(104) XRD peaks than samples sintered with a single air (800 °C). ratio (compare 1.31 vs. 0.95). Indeed, the (003)/(104) peak ratio of this Example 2 is much higher than the two NCA80 samples sintered at higher temperature (850° C.) in pure O ₂ as shown in Table 1.

The x-ray diffraction (XRD) patterns for NCA80 sintered under different conditions are also provided in FIG. 3 for comparison. This comparison demonstrates the difference in peak intensity that exists between the two NCA80 samples. Both samples did not show any presence of an impurity phase from Li ₂ O/Li ₂ CO ₃ .

Table 2: Sintering conditions and peak ratio (003)/(104) for NCA80.

Example 3 - Li _{1 . 05} Ni _{0 . 9} Co _{0 . 05} Al _{0 . 02} Mn _{0 . 025} B _{0 .} Manufacturing and testing of ₀₀₅ O ₂ (NCMA90)

Nickel oxide (NiO) (˜325 mesh, 99%) was purchased from Sigma Aldrich, USA. An NCMA90 sample was prepared by ball milling 38.8 grams Li ₂ CO ₃ , 67.22 grams NiO, 4.01 grams Co ₃ O ₄ , 1.56 grams Al(OH) ₃ , and 0.309 grams H ₃ BO ₃ in water. The solid/water mass ratio was 4/6. A total of 160 grams of 2 mm ceramic beads were added to the dispersion and the dispersion was milled for 5 hours. The target composition is Li _{1 . 05} Ni _{0 . 9} Co _{0 . 05} Al _{0 . 02} Mn _{0 . 025} B _{0 . 005} O ₂ . A slight excess of lithium carbonate was added to compensate for the lithium loss expected to occur during the sintering process.

After milling, the dispersion was spray dried in a benchtop spray dryer. After drying, the powder was first sintered in air at 500°C for 2 hours and then at 850°C for 10 hours. Then, the air-sintered powder was transferred to a glass tube and sintered again at 750° C. for 10 hours in a flowing state of pure O ₂ . X-ray diffraction (XRD) patterns were measured using a benchtop Rigaku X-ray machine.

The sintering conditions and corresponding (003)/(104) peak ratios are shown in Table 3. NCMA90 samples exposed to the pure O ₂ post-sintering step showed an increase in the (003)/(104) peak ratio compared to samples sintered in air only (0.91 → 1.01 comparison). This example shows that the use of pure O ₂ posttreatment increases the (003)/(104) peak ratio even at 90 mol% of the Ni content, but the (003)/(104) peak ratio values are lower for samples with lower Ni content. This demonstrates that this is not the case at the same level as observed in (see NCA80 in Tables 1 and 2).

Table 3: Sintering conditions and peak ratio (003)/(104) for NCMA90.

According to another aspect of the present disclosure, a cathode active material for use in an electrochemical cell is disclosed. This material formed according to the process described above and in FIG. 1 generally includes the formula described by Formula F-1. The electrochemical cell may be selected to be a lithium ion or lithium battery having a high nickel lithiated metal oxide or active cathode material used for at least a portion of one of the electrodes.

Within this specification, embodiments have been described in such a way as to enable a clear and concise description, but it is intended and to be appreciated that embodiments may be variously combined or separated without departing from the invention. For example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

Those skilled in the art will, in light of this disclosure, appreciate that many changes can be made in the specific embodiments disclosed herein and still obtain a like or similar result without departing from or exceeding the spirit or scope of the disclosure. One skilled in the art will further understand that any properties reported herein represent properties that are routinely measured and can be obtained by a number of different methods. The methods described herein represent one of these methods, and other methods may be utilized without exceeding the scope of the present disclosure.

The foregoing description of the various forms of the present invention has been presented for purposes of illustration and description. It is not intended to completely limit or limit the invention to the precise form disclosed. Numerous modifications or variations are possible in light of the above teachings. The forms discussed have been chosen and described to provide the best illustration of the principles of the invention and its practical application, thereby enabling those skilled in the art to utilize the invention in a variety of forms and with various modifications suited to the particular use contemplated. . All such modifications and variations are within the scope of the invention as determined by the appended claims when construed in accordance with the scope to which they are fairly, legally and equitably entitled.

Claims (20)

A process for producing a high nickel lithiated metal oxide comprising:
a. selecting one or more nickel precursors;
b. providing at least one non-corrosive lithium salt;
c. delivering a plurality of metal oxide or hydroxide precursors;
d. mixing together one or more nickel precursors, one or more non-corrosive lithium salts, and a plurality of metal oxide/hydroxide precursors to form a mixture comprising:

where x = 1.0 - 1.1, 0.80 ≤ y ≤ 0.90, 0.03 < z ≤ 0.15, and 0 ≤ ≤ 0.05, M is Co or Fe; and N is Al, Mn, Fe, Ca, Mg, Ti, Cr, Nb, Mo, W, B, or mixtures thereof, provided that when M is Co, N may be Fe;
e. Forming a powder by sintering the mixture at a temperature of 750 ° C. or higher in an air environment in the first sintering step; and
f. In the secondary sintering step, the powder is sintered in an O ₂ environment at a temperature of 750° C. or less to form a high nickel lithiated metal oxide. The process of claim 1 , wherein M in formula (F-1) is cobalt. 3. The process according to claim 1 or 2, wherein y in formula (F-1) is 0.80 < y < 0.87. 4. The process according to any one of claims 1 to 3, wherein y in formula (F-1) is 0.80 < y < 0.85. 5. The process according to any one of claims 1 to 4, wherein N in formula (F-1) is Al. 5. The process according to any one of claims 1 to 4, wherein N in formula (F-1) is Mn. The process according to any one of claims 1 to 4, wherein N in formula (F-1) is Al and Mn and the molar ratio of Al/Mn is from 0.99/0.01 to 0.01/0.99. The method according to any one of claims 1 to 4, wherein N in formula (F-1) is Al, Mn, and one of Fe or Mo, and the molar ratio of Al/Mn/(Fe-Mo) is 0.99/0.05 /0.05 to 0.05/0.99/0.05 to 0.05/0.05/0.99. 9. The process according to any one of claims 1 to 8, wherein the O ₂ environment of the second sintering step is pure oxygen. 10. The process according to any one of claims 1 to 9, wherein the first sintering step has a temperature of ≥ 750 °C and ≤ 1000 °C. 11. The process according to any one of claims 1 to 10, wherein the temperature in the first sintering step is ≥ 800 °C and ≤ 950 °C. 12. The process according to any one of claims 1 to 11, wherein the temperature in the first sintering step is > 850 °C and < 900 °C. 13. The process according to any one of claims 1 to 12, wherein the first sintering step is performed with a sintering time ranging from 2 hours to 24 hours. 14. The process according to any one of claims 1 to 13, wherein the temperature in the second sintering step is ≤ 750 °C and ≥ 700 °C. 15. The process according to any one of claims 1 to 14, wherein the secondary sintering step is performed with a sintering time ranging from 2 hours to 24 hours. 15. The process according to claim 14, wherein the sintering time of the second sintering step is longer than the sintering time of the first sintering step. A cathode active material for use in a battery comprising a material formed according to the method of any one of claims 1 to 16 having a formula according to (F-1):

where x = 1.0 - 1.1, 0.80 ≤ y ≤ 0.90, 0.03 < z ≤ 0.15, and 0 ≤ ≤ 0.05, M is Co or Fe; And N is Al, Mn, Fe, Ca, Mg, Ti, Cr, Nb, Mo, W, B, or a mixture thereof, provided that when M is Co, N may be Fe. The method of claim 17, wherein the sintering temperature of the second sintering step is equal to or lower than the sintering temperature of the first sintering step;
and the O ₂ environment of the second sintering step is pure oxygen. A lithium ion or lithium battery comprising a cathode active material as one of the electrodes, wherein the cathode active material is formed according to the process of any one of claims 1 to 16, and the high nickel lithiated metal oxide according to (F-1) A lithium ion or lithium battery having the formula:

where x = 1.0 - 1.1, 0.80 ≤ y ≤ 0.90, 0.03 < z ≤ 0.15, and 0 ≤ ≤ 0.05, M is Co or Fe; And N is Al, Mn, Fe, Ca, Mg, Ti, Cr, Nb, Mo, W, B, or a mixture thereof, provided that when M is Co, N may be Fe. The method according to claim 19, wherein the sintering temperature of the second sintering step is equal to or lower than the sintering temperature of the first sintering step;
A lithium ion or lithium battery in which the O ₂ environment of the second sintering step is pure oxygen.

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